Icing compositions comprising carboxymethyl dextran and method of producing the same



ICING COMPOSITIONS COMPRISING CARBOXY- METHYL DEXTRAN AND METHOD OF PRO-DUCING THE SAME Harry A. Toulmin, In, Dayton, Ohio, assignor, by mesneassignments, to Midland Chemical Corporation, Dayton, Ohio, acorporation of Delaware No Drawing. Application June 7, 1954, Serial No.435,088

14 Claims. (Cl. 99-139) This invention relates to improvements in icingsfor use on bakery products.

Various types of icings are known the basic ingredients of which aresugar and water but which may comprise supplementary ingredients such asfats and shortening, egg whites, skim milk powder, chocolate andflavoring ingredients as well as, in some cases, flour or cornstarch asa bodying agent. Some icings consist essentially of egg whites andsugars.

It is the common practice to include in the icing composition astabilizer which improves the texture and appearance of the icing andmay improve its keeping property.

Icings comprising flour, cornstarch or other known bodying agents arenot entirely satisfactory, for one reason or another. Furthermore, theknown stabilizers,

such as alginic acid derivatives, are less efiective than is desirable.

One object of this invention is to provide new icing compositionscomprising sugar and a thickening and bodying agent which is also astabilizer for the icing, improves the texture and appearance, andimparts plasticity to the composition so that application thereof tocakes or the like is facilitated.

Another object is to provide a thickening and stabilizlected dextran anda carboxymethylating agent are reacted together in an aqueous alkalinemedium whereby the carboxymethyl group is substituted for one or morehydroxyl groups in the dextran molecule. Suitable carboxymethylatingagents are chloracetic acid, sodium chloracetate or chloracetamide. Thereaction is carried out in an aqueous solution of a strong alkali metalhydroxide such as sodium, potassium or lithium hydroxide. Preferably,the dextran is treated, in aqueous solution or suspension, with anexcess of sodium or potassium chloracetate in the presence of an excessof sodium or potassium hydroxide at a temperature of 50 C. to 100 C. forten minutes to two hours.

chloracetate'to dextran is between 2:1 and 12:1, the molar ratio ofsodium hydroxide or potassium hydroxide to dextran is between 5:1 and15:1, and the molar ratio of the water to dextran is between 20:] and120:1. The carboxymethyl dextran obtained under these conditions has aD. S. (degree of substitution or average Also preferably, the -molarratio of sodium chloracetate or potassium.

number of carboxymethyl groups per anhydroglucopyranosidic unit) of lessthan 1:1 to 3: 1.

The reaction product is .a viscous mass comprising the sodium or"potassium salt of the carboxymethyl dextran. The salt may beprecipitated from it by a non-solvent therefor, as by means of anywater-miscible alcohol, e. g., methyl, ethyl, propyl,'isopropyl oft-butyl alcohol, or by means of a water-miscible ketone such as acetone.

The free carboxymethyl dextran may be recovered from the salt by mixingthe latter with water, acidifying to pH about 2.0, and precipitating theether by means of acetone or a water-miscible alcohol as specifiedabove. The pH of 2.0 is not critical and other acid pH values may beused. However, the highest yields of the free ether have been obtainedby precipitation at pH 2.0.

The dextran carboxymethylated may be obtained in various ways. Usually,it is biosynthesized from sucrose by a microorganism of the Leuconostocmesenteroides or L. dextranicum types, or the enzyme thereof.Microorganisms which may be used include those bearing the followingNRRL (Northern Regional Research Laboratory) designations: Leuconostocmesenteroides B-512, B419; B1146, B-1190, B-742; 13-1191, B-1196,B-1208,"B-1216, B-1120, B-1144, B-523 Streptobacterium dextranicumB-1254 and Betabacterium vermiforme B1139.

The dextran is produced by introducing a culture of the microorganism,or the enzyme isolated from the culture by filtration, to an aqueoussucrose-bearing nutrient medium and holding the mass until the dextranis synthesized in maximum yield, after which the dextran is precipitatedby the addition of a water-misciblealiphatic alcohol or acetone; Theprecipitated nativedextran is purified andpreferably reduced to finepowder form for 'carboxymethylation. This native? dextran asconventionally produced is normally characterized by a very highmolecular weight which has been calculated to be in the millions. -Itmay be carboxymethylated at the native molecular weight or it may bepartially by.- drolyzed to lower molecular weight dextran in anysuitable way, as by acid or enzyme action, and then carboxymethylated.

Relatively small amounts of are effective in stabilizing the icingcompositions. However, the presently preferred ether is one derived frommicrobiologically produced, unhydrolyzed,- native high molecular weightdextran such as native, unhydrolyzed B-512 dextran or dextran equivalentthereto and containing an average of from2.0 to 3.0 carboxymethyl groupsper A. G. U. Such ethers are preferred because I of the strikingeffectiveness thereof, as bodying and stabilizing agents for the icingcompositions, in extremely small amounts. Thus, a marked increase isobtained by the addition of these preferred ethers in amounts as low as0.01% to 0.5% by weight. The carboxymethyl dextrans are much moreeffective as thickneners than available carboxymethyl celluloses. Aboutfive times more of the carboxymethyl celluloses is required to produce agiven viscosity increase than is required when the carboxymethyl dextranis used.

The carboxymethyl dextran may be mixed with the other ingredients of theicing composition in the dry," powdered form, as a solution ordispersion; in'water, or 1.1-

v -PatentedApr. 23', 1957 3 the carboxymethyl dextran in whichthe-.partsare .by =weight, are illustrative of somespecificnicingicompositions. in .accordance...with the..inven-. tion.

I Percent Water 22.0 Sugar..- 77.8 Carboxymethyl:dextran froml. m. B-512native dextran, average. D.'S.,- -2;8 0.2

TheWater and sugar aremixedtogether, and the car-r boxymethyl dextran,is then incorporated with stirring...

Percent naming; I f 0.4 Carboxymethyl: L; m. B75 l2..dextran. averaged).

This composition is ,stable,; with little coalescence or separationofthe fat, and, has a uniform, smoothtexture.

and. appearance.

III

Percent Sugar 74.2. Water 22.7 Egg white liquid 2.6 CarboxymethylL. m.B-1-5l2, native dextran, average The compositions containing thecarboxymethyl dextranmay be applied to bakery products in-any "suitablelimit the invention except; as it is defined inthe appended claims.-

Whatis claimed is:

1. An icing composition for bakery products comprising sugar, and as astabilizing-and bodying aid,--a small amountof-carboxymethyldextran:containing an average of "about-2.0-'to3.0carboxymethyl groups per anhydro.

glucopyranosiclic unit." a

2. A icing composition for bakery products-comprising sugar, 'andas astabilizing and bodying aid, from about 0.01% to 0.5% by'weigbt of-acarbmiymethyl ether of a microbiologically produced native, unhydrolyzeddexnan-containing anavcrage of-from 2.0 to 3.0 carboxymethyl groups perauhydroglucopyranosidic unit of the dextranfl 3. An icing compositionfor bakery products comprising a mixture of sugar, water and, as astabilizing and bodyiug aid,'a smallamount of carboxymethyl dextrancontaining an average of about 2.0 to 3.0 carboxymethyl groups peranhydroglucopyranosidic unit.

4.,An icing-composition for bakery products comprising a mixture ofsugar, water and, as a stabilizing and bodyingaid, from 0.01% to 0.5%'-by weight of a car boxymcthyl ether. of amicrobiologically producednative unhydrolyzed dextran containing an averaged-2.0 to 3.0

V 4 carboxymethyl groups per anhydroglucopyranosidic unit ofthe.dextran.-

5. An icing composition for bakery products comprising sugar, water,shortening, salt, flavoring and, as stabilizing and bodying agent, asmall amount of carboxymethyl dextran containing an average of about 2.0to 3.0

carboxymethyl groups per anhydroglucopyranosidic unit.,

6.:.An icing composition for bakery products comprising sugar, water,shortening, salt, flavoring-and, as a stabilizing and bodying agent,from 0.01% to 0.5% by Weight'of a carboxymethyl ether of amicrobiologically produced, native-unhydrolyzed.deXtran containing from2.0 to 3.0 carboxymethyl groups per anhydroglucopyranosidic unit .of thedextran.

7. An icing composition for use. on bakery products comprising sugar,egg White, liquid and, as stabilizing and bodying aid, a small amount ofcarboxymethyl dextran containing an average of about 2.0 to 3.0carboxymethyl "groups-per anhydroglucopyranosidic unit;

8. An icing composition for use-on bakery products comprising sugar, eggwhite liquid and, as stabilizing and bodying aid, from 0.01% to 0.5%by-weight of a carboxymethyl I ether-- of 'microbiologically produced,native unhydrolyzed dextrancontaining an average of from 2.0 to 3.0carboxymethyl groups per anhydroglucopyranosidic unit of-.the dextram 9.An icing composition for use on bakeryproductscomprising: sugar;flavoring and,- as stabilizing and-bodying-aid,- a smallamount ofcarboxymethyl dextran -containing-an average/of" about 2.0 to 3.0'carboxymethyl groups per anhydroglucopyranosidic unit.

10. An icing'composition -for use on bakery products comprisingsuganfiavoring and, asstabilizing and bodying=-aid,- from-0.01% to 0.5%by-weight of-a carboxymet-hyl-ether-ota microbiologically produced,native unhydroiyzed dextran containing an average of 2.0 to 3.0

carboxymethylgroup per anhydroglucopyranosidic unit of the-dextran.-

11. The-methodof stabilizing and-bodying an icingcomposition-ior bakeryproducts comprising sugar which comprises-miXing- -withthe icingingredients a small amount of a carboxymethyl deXt-ran containing anaverage of about-2.0 to 3.0 carbo-xymethyl groups, per anhydroglucopy-ranosidic' unit.

12; The method of stabilizing and-bodying an icing composition. forbakery product comprising sugar and water-which comprise mixing with theicing ingredients a small amountoficarboxymethyl dextran containinganaverage of about 2.0 to 3.0carboxymethyl-groups=peranbyd-roglucopyranosidic unit.

1.3.The4nethod of stabilizing and bodying an icing composition forbakery products comprising sugar, Water,

shortening-, salt, and flavoring, which comprisesmixing .witlrth'eicingingredients a small amount of carboxymethyl dextran containingan'average of about 2.0 to'3.0 carboxymethylagroupsperanhydroglucopyranosidic unit.

l4.-.Themethod of stabilizingand bodyingan. icing- Referencesflitedrinthe file of this patent. UNITED STATES PATENTS 2,089,217 Iviahoney Aug.10,1937 2,409,816 Wadsworth et a1. Oct. 22, 194.6. 2,602,082 Owen July1, 1952 2,609,368 Gaver Sept. 2, 1952

1. AN ICING COMPOSITION FOR BAKERY PRODUCTS COMPRISING SUGAR, AND AS ASTABILIZING AND BODYING AID, A SMALL AMOUNT OF CARBOXYMETHYL DEXTRANCONTAINING AN AVERAGE OF ABOUT 2.0 TO 3.0 CARBOXYMETHYL GROUPS PERANHYDROGLUCOPYRANOSIDIC UNIT.